Azo compounds and process for coloring therewith



ii eietcoi H, 1941 WEIWG T rnoonss roe here Nomec hi. Mcltally nml .ioeeph iclrey, itoeh ester, N. i nsslynors to Eastman Ketch Gore- Rochester, N. Y n, corporation oi New horlicotlon tie it, with,

erinl Ito errors (iii. ti ht) invention relates to new eryl oeo hot else moezl ecetel roops such cs: pools cool their application to the eel; oi eyeinc 0cm 061m other or coloring. More particularly, the inrention to H H H P letes to eryl monoazo dye compounds chcrocter CHPC CHM: CHPC U icetl in thet they contain an ecetel creep lirhecl GHi 00m am i to the eryl dye nucleus through o nitreoen otoin ocamogm 0.3mm 00mm which is o nueleer sehshtnent oi the eryl elye CE CH C CH O nucleus one the npphcctioh oi the necleer hen- V snliono one eye compoohols oi the intention B 'B i 1} 0mm i m m to the colerotion oi orcehic tlerireticce oi cello Hm m lore. onol h reenic olerivetives oi cellulose ere chereeter: ieerl hy oh inereot oty' tor the iloilni cetteri ehe'i wool tiyes, especielly the oriilhery teeter colo hie riyes. heconee oi this, ithec hech heceeceiw i to clerelop new eye cenipoonee ooltohie tor the 0mm rlyeieo or colerctien oi rhetoric-ls snch es tertile ior ereniple. heeterlels, emetic oi or cohtoinino on orwonic tie- "the lost three groups just given, strictly specie-=- riyetiye oi cellulose. it is, eccorriineimhn ohiect inc, ore prohehly more properly reierrec'i to to W oi my intention to provide it new close oi ere hotel groups. The expression on ecetei creep," siiitciile tor the elyehio; or coloretion oi or--- it o reetricteel mooning is epplieti thereto, prehe cohic cleriyetires oi cellulose. hnother ehiect is ioly oloes hot include o hotel group eltheueh it is to preritie or process tor the dyeinw or, coloretien not uncommon to reeercl hotel es snheeneric to oi ereonic oeriyetires oi celhileee, it iorther ecetel. 'i'hot this is so is reoclily epperent irons oloject ie to proyiele as, process ierthe celerotlon the 'ieot thet the term hotel is eeiineel hy m oi erronictierlvatives oi cellnlece in which the Wehsters New linterriotionel Dietitonery-ilnthe or rlyee ere epeiiecl directly to the inoteriel nlerlocee teel eci-iilth, es Chem. ilri ecetol iihoerrroihc coloration from on oeeeooc eespen eeriyeoi iroin e lretone, oi the eeeerel iorrnolo rich. it still iiirther oloject ie to preiince iyeince X (QR We on erc'enic rierirotiyee oi cellulose which ore oi m cocci iestness to light one woehino.

'li yplcol oreenic rieriretirec oi oelloloce inclecle Y Hill m' 'il i tie Wei its m ifltoili t i'tcilll- For the purpose oi the present invention, since W lose ercenic ecicl esters, such he celinloee'ecetete, the hetei creep moy he employee in the prepore- 3e cellulose iornicte, cellulose propionete, or cellii time of one rlye compounds soitohle tor the olyem lose hntyrote, one the hydroiyzeo on well to the his or coloration oi oreeeie eerirotiyes oi cellonnhyoirolyceii mined oreic cold esters oi cellolose, it will he understooe thet the erpressien on lose, siich es cellulose ocetete propionete, cellii social group is so eerie to hotel creeps. lose ocetcte-hutyrete, encl the cellulose others, The nncleer noo-solioneteel ory'l eeo iiye conem M such es methyl cellulose, ethyl cellulose or hemyl pounds oi our invention constitute releehle eyes cellulose, tor the coloretion oi oree-oic olerivetires oi celloihe eryl coo oiye compounds oi cor invention lose yielcline sherles roneinc from hlne yreeri to here the eenerel iormele: purple eml iroln yellow to red. These coinpeinmele i similarly possess epplicetion for the coloretion oi wool one silir. end yieltl the some or cehereliy Wh i ih R lfelffl'efifillit e m i i l oi on him similor sheoles thereon. llomponnos oi the ohore niiclens one iii represents e meinhe eelecteti irons enerol iorrnulo which eontcin o necleer soiienie the creep consisting oi o. phenyltresiooe encl o eciol group can likewise he preporeol in lemon hephthelene reslrhre continuing on oeetel group ieshion. These compounds possess little or no 5 m limited to the nucleus throiieh or. nitrogen swi utility tor the coloration oi organicolerirotives oi which is o necleer sohstitueot oi one member. vtcliiiiete h a be p y d to color t tile Adventogeonsly it one R1 are phenyl poo-lei, moteriels such es silk and wool. For the dyeing in oreler thet our invention mey he celerly o or oreonie deriireisives oi cellulose, such as eelln- 55 oersteod, it will he noted that the expression on lose ocetete silir, nucleor hon-sillioneteol eoirr- W ecetel group" inoiiides not only the oeetei creep pounds wherein R1 is a, phenyl residue ere genoczm erolly coheidierchly more light test then those CH g compounds wherein R1 is a, nophtheieee resitine. V The eryl one rlye compounds oi our invention m OCrHc can he conveniently prepereoi hy diorotleine on arylamine and coupling the diazonium compound resulting with a phenyl or naphthalene coupling component containing an acetal group linked to its nucleus through a nitrogen atom which is a nuclear substituent thereof. The phenyl or naphthalene coupling component may be further substituted in its nucleus, as will be more fully apparent hereinafter, but it will be understood that its coupling position must not be blocked.

Arylamines that can be employed in the preparation of the azo compounds of our invention include, for example, aniline, nitro substituted anilines, such as p-nitroaniline and 2L4-dinitroaniline, halogen substituted anilines, such as pchloroaniline, o-chloro-p-nitroaniline, o-bromoaniline, p-iodoaniline. and 2,4-dichloroaniline, alkyl substituted anilines such as o-methylaniline, p-ethylaniline, o-p-methoxyethylaniline and ochloro-p-methylaniline, alkoxy substituted anilines, such as p-methoxyaniline, o-p-methoxyethoxyaniline andp-butoxyaniline, keto substituted anilines such as p-aminoacetophenone and p-aminophenyl propyl ketone, sulfonated anilines such as 1-amino-2-sulfonic benzene and l-amino- 2-sulfonic-4-nitrobenzene and naphthylamines such as enaphthylamine, fl-naphthylamine, 1- aminol-hydroxynaphthalene, l-amino-Z-sulionic naphthalene, 1-amino-4-nitronaphthalene, and 1-amino-8-hydroxynaphthalene. Further, arylamines such as p-aminobenzophenone, oaminobenzophenone, p-aminodiphenylamine, and p-aminoazobenzene can be used. As a further illustration of the arylamines which can be employed in the preparation of the azo compounds of our invention reference may be had to our U. S. Patents Nos. 2,107,898 and 2,115,030, issued February 8, 1938, and April 26, 1938, respectively, wherein additional suitable arylamines are disclosed. It will be clearly understood, however, that the arylamines, disclosed herein are given by way of example and are not intended to be limitative of the invention. Any of the arylamines disclosed herein may be diazotized and the diazonium compound resulting coupled with any of the coupling components disclosed herein to obtain dye compounds of the invention.

The coupling components ordinarily employed in the preparation of the azo compounds of our invention may be represented by the general formula:

R; Rt Bla r-oar -R,

wherein R1 represents a phenyl or naphthalenegroup, wherein R3, In and R have the meaning previously assigned to them. R1 may be substituted as has been previously indicated.

The following examples illustrate the preparaof the dye compounds of our invention:

Example 1 36% hydrochloric acid. Theresulting solution is cooled to a temperature approximating 0-5 C. and the amine diazotized, while maintaining this temperature, by the addition, with stirring, of a water solution of 6.9 grams of sodium nitrite.

20.9 grams of the diethyl acetal of phenylaminoacetaldehyde, grams of glacial acetic acid and 200 grams of water are mixed and the diazonium solution prepared above is added, with stirring. During the coupling reaction which takes place, sodium acetate is added from time to time to keep the reaction mixture neutral to Congo red paper. Upon completion of the coupling reaction, the dye compound formed is precipitated by the addition of water, recovered by filtration, washed with water and-dried. The dye compound formed has the formula:

can be obtained. This compound yields a reddish shade on cellulose acetate sills.

Example 2 13.5 grams of p-aminoacetophenone are diazotized in the usual manner and coupled with 23.7 grams of the diethyl acetal of ethylphenylaminoacetaldehyde. The dye compound formed which may be recovered in accordance with the method described in Example 1 has the general formula:

0 CzH O C 2H5 l z a O 01H:

H/ CHaCON: Orr-omo OGZHB and colors cellulose acetate siLk an orange shade of good iastness to light and washing.

Example 3 18.3 grams of 1-amino-2,4-dinitrobenzene are diazotized and coupled with 31.9 grams of the dip-methoxyethyl acetal of e-naphthylamine. The dye compound obtained has the formula:

and colors cellulose acetate silk a reddish purple shade.

Example 4 26.2 grams of 1-amino-2,-dinitro-6-bromobenzene are diazotized and the diazonlum compound Icrmed is coupled with 33.2 grams of the di-fi-methoxyethyl acetal or methyl-e-naphthyl- Amine Coupling component ggg gaz fi H O 01H; 1-en1lno-4-cl11orobenzene (11) N-C Hz-C Orange-yellow.

0 CzHo Diethyl acetal of a-naphthyl-aminoaoetaldebyde CH H A} Do (12) N-CHz- 0 01m Yellow.

0 C 1H5 C H:

Diethyl ketal o1 3-methoxyphenylamlnoaeetone H Do (13 N-cm-c o 0,3, D0.

Dlethyl ketal o! wphenylaminoaeetophenone I H 0 02H: Do (14) NCH-.C Orange.

' O CzHu 0H Dlethyl aeetal of 8-hydroxy-q-naphthylamine Q 0 C H:

0 C2Hs Do (15) N-C Ha-C Yellow.

0 0111s CH:

Diethyl aeetal of 2,Mlmethoxy-benzylphenylaminoaeet aldehyde 0 CaHs (16) NCH:-C\ Do.

Dlethyl acetal of dlphenylaminoaeetaldehyde H: H: 1 /C\ /C H: D0 (11) ON c-o Do.

H: HI

0 Q2315 CH:--C\

Diethyl acetal of cyclohexylphenylaminoaoetaldehyde /OH:CO C 2H5 Do 8) O-N I Do.

0 1110-0 CzH:

p-Amlnoaeetophenone 1 to 18 above Orange to red. p-Nltroanlline n Orange to blua. p-Nltro-o-bromoani1ine .do Red to blue. 2,4-dinitroani1ine Rublne to green-blue. 2,4-dlnitr0-6-br0m0anillnn do Do. 2,4-dlnitro-8-chloroani1ine n .u- Do. 2,4.Mrlnltroaniline n Do. 1-am1no-2-nltro-4-aoetobenzene.... n Orange to green-blue. 4-nltro-2-hydroxyanfllm r 0 Pink to blue. pAminoazobenzen do Orange to blue.

e coupling components employed in the preparation of the azo dye compounds of our invention ofler little or no difliculty as regards their preparation and may be prepared in any 5 suitahle manner. Compounds o! the seneral iormula:

vvherein R1 is a phenyl or naphthyl nucleus and its and Breach represents an alkyl group can he prepared by reacting a compound having the eeneral iormula RrNH: wherein R1 represents a 115 phyl or naphthyl nucleus with a compound ha i i the aeneral formula H/R4 n-cm-o Eli Oltr vvherein it is a halogen atom such as corine methods ovvn tor the introduction oi such suhetituent l neups. idimilarly, said hydroyen atoin may he replaced hy a H/O Ry -CHr-C p nup, hy the use all two instead parts oi IaE/OR .iiF-CEhr-C U-Ry in the reaction that set iorth.

@ouplhay compounds have the iormuia:

lRr ORi R;N-ClEIyii ()Ry wherein iiti is phenyl or naphthyl nucleus, he is hydroren, all, aryi, hydroi or araliml, ids 55 is allvyl or aryl and its and lit-s each repreaen aiiryi, can he prepared hy treatiny an aryl :1, havinp the yeneral iormula:

at one mole H awn-m W vvith a oompod haviny the yeneral iormula:

Hi 01% :a-cni-i @iti iiii

to e following example illustrates the preparei the reaction is removed lei-- tion of a coupling component suitable for use in the preparation of the azo compounds of our invention. i

Preparation of the diethylactal of ethylphenyluminoacetaldehz'lde 1211 grams of ethylaniline are placed in a flask with lilh grams oi anhydrous sodium bicarbonate. The mixture resulting is heated with stirring to a temperature of 120-130 C. and then 243 grams l0 oi hromoacetal are added dropwise. Upon completion oi the reaction which takes place, the reaction product is removed hy extraction with alcohol and iollowing-removal oi the alcohol hy evaporation, ior example, the reaction product is 5 distilled under reduced pressure to give a good yield oi the desired compound.

%y the suhstltution oi aniline for ethylaniline an CHe OCzHt m-cHi-c OCzHn ior hromoacetal in the above reaction, the hotel compound, 7

(311a n l 001m 1 I N--0Hi--0 I OCsHn can he prepared. 5

3 The use dye compounds oi our invention are,

I tor the most part, relatively insoluble in "water.

These compounds, which are insoluble in Water, may he advantageously employed for the direct dyeing oi tertile materials hy'erindine the dye M to a line povvder, intimately miriine it with a suitable dispersing or soluhiliaina agent and adding the resultina mixture to Water or a dilute solution at soap in water to form an aqueous dyehath, l hlloivinu this imov/n preparation oi the dyehath, M the teutile material to he dyed may he added to the dyehath and the dyeina'operation conducted in lrnovvn iashion. The dye compounds oi our invention which are water soluhle do not, oi course, require the use oi a dispersing or soluhilm iuinp apent hut may he applied to silir, Wool and (dependinu on the nature and position oi the crater soluhiliaina el'oup) organic derivatives oi cellulose tentile materials irom an aqueous solu-- tion oi the dye which may contain. salt. For a more complete description as to how. the are dye compounds oi our invention may he employed in dyeing or colorine operations, reference may he had to our United idtates Letters Patent No.8 hiliihdh, issued iipril 2d, lhdd. w We claim:

l. e are dye compounds havina theaeneral ioiula:

wherein it represents the residue oi a memher sees lected irom the eroup consistinir oi an aryl nu-' cleus oi the henaene series, an aryl nucleus at the naphthalene series and an and henaene nucleus and he represents a mom-her selected from the aroup consistin'a" at a phenyl nucleus and a to naphthyl nucleus said memher containing an acetal uroup linired to its nucleus through an. amino nitroitcn atom vvhich is a nuclear suhstitu ent oi the said memher andlvvhich is in para position to the bond. 7 r

.2. The azo dye compounds having the general formula:

RN=NR1 wherein R represents the residue of a member selected from the group consisting of an aryl nucleus of the benzene series, an aryl" nucleus of the naphthalene seriesand an azo benzene nucleus and R1 represents a member selected from the group consisting of a phenyl nucleus and a naphthyl nucleus said member containing a R5 group, wherein R and R each represents an alkyl group, linked to its nucleus through an amino nitrogen atom which is a nuclear substituent of the said member and which is in para position to the azo bond. I 1

3. The monoaz'o dye compounds having the general formula:

RN=N-R1 wherein R represents the residue of a phenyl nucleus and R1 represents a phenyl nucleus containing an acetal group linked to its nucleus through an amino nitrogen atom which is a nuclear substituent of said phenyl nucleus and which is in para position to the azo bond.

4. The monoazo dye compounds having the general formula:

R N=N---Ri wherein R represents the residue of a phenyl nutaining a cleus and R1 represents a phenyl nucleus conwherein R represents the residue of a phenyl nucleus and R1 represents a phenyl nucleus containing" an acetal group linked to its nucleus through an amino nitrogen atom which is a nuclear substituent of said phenyl nucleus and which is in para position to the azo bond:

6. The process of coloring an organic derivative of cellulose which comprises applying thereto a nuclear non-sulfonated aryl monoazo dye compound having the general formula:

RN=NR1 wherein R represents the residue of a phenyl nucleus and R1 represents a phenyl nucleus containing a 0 R -H -.CH|C

'OR1 A: group, wherein R4 and R5 each represents an alkyl group, attached to its nucleus through an amino nitrogen atom which is a nuclear substituent of said phenyl nucleus and which is in. a para position to the azo bond.

7. The process of coloring an' organic acid ester of cellulose'which comprises applying thereto a nuclear non-sulfonated aryl monoazo dye compound having the general formula:

wherein R-represents the residue of a phenyl nucleus and R1 represents a phenyl nucleus containing an acetal group linked to its nucleus through an amino nitrogen atom which is a nuclear substituent of said phenyl nucleus. and

, alkyl group, attached to its nucleus through an amino nitrogen atom which is a nuclear substituent of said phenyl nucleus and which is in a para position to the azo bond,

9. Material made of or containing an organic derivative of cellulose and in which said organic derivative of cellulose is colored with a nuclear non-sulionated aryl azo dye compound having the general formula: I

wherein R. represents the residue of a member selected from the group consisting of an aryl nucleus of the benzene series, an aryl nucleus of the naphthalene series and an azo benzene nucleus and R1 represents a member selected from the group consisting of a phenyl nucleus and a naphthyl nucleus said member containing an acetal group linked to its nucleus through an amino nitrogen atom which is a nuclear substituent of the said member and which is in para position to the azo bond.

10. A cellulose acetate colored with a nuclear non-sulfonated aryl azo' dye compound having the general formula:

RN=NR1 wherein R represents the residue of a member selected from the group consisting of an'aryl nucleus of the benzene series, an aryl nucleus of the naphthalene series and an am benzene nucleus and R1 represents a member selected from the group consisting of a phenyl nucleus and a naphthyl nucleus said member containing an acetal roup linked to its nucleus through an amino nitrogen atom which is a nuclear substituent of the said member and which is in para position to the azo bond.

11. A cellulose acetate colored with a nuclear non-sulfonated aryl monoazo dye compound having the general formula:

wherein R represents the residue of a phenyl nucleus and R1 represents a phenyl nucleus containing an acetal group linked to its nucleus through an amino nitrogen atom which'ism. nuclear substituent of said phenyl nucleusand which'is in para position to the azo bond.

JAMES G. M'cNALLY.

JOSEPH B. DICKEY. 

